Process for the production of a brilliant bluish-red chlorine-resistant dischargeable ground on cellulose fabrics



United States Patent Claims. icl. s-ss It is known how to produce brilliant bluish-red discharge grounds on cellulose textile fabrics with the aid of suitable reactive dyestuffs. Though these grounds can be discharged white, they are not resistant to chlorine. Although, on the other hand, brilliant bluish-red discharge grounds which are resistant to chlorine can be prepared with different reactive dyestuffs, these can however not be discharged White. In dyeing technology, it has furthermore not hitherto been possible to prepare from ice colour dyestuif coupling components and, optionally stabilised, diazonium compounds grounds capable of being Ice colour dyestuffs can by the use of diazoamino discharged.

be prepared by calico printing compounds from diazotised 1-amino-Z-methoxy-benzene-S-carboxylic acids anilide and secondary o-aminophenyl-carboxylic acids, acting as stabilizers, and ice colour dyestuif coupling components. However, it is not the normal custom to achieve unidyeings by a printing procedure and this is difficult to carry out in practice.

In technology, there has for a long time been a requirement for a brilliant bluish-red discharge ground capable of being discharged and resistant to chlorine which can be prepared during a continuous dyeing operation in acocrdance with the padding process. The known processes which have hitherto been reported do not offer the possibility of satisfying this requirement.

It has now unexpectedly been discovered that a brilliant bluish-red discharge ground resistant to chlorine can be obtained on cellulose fabrics when natural or regenerated cellulose is dyed with a mixture of substantially equimolar amounts of 1-(2',3-hydroxynaphthoyl-amino)-2-methoxy- S-chlorobenzene and the diazoamino compound obtained from diazotised l-amino-2-methoxy-benzene-5-carboxylic acid anilide and a secondary o-aminophenyl-carboxylic acid, optionally in the presence of suitable assistants, and it is then developed by the action of acidic or neutral steam.

In detail, the dyeing is carried out by preparing a mixture of approximately equimolar amounts of 1-(2',3-hydroxynaphthoyl-amino)-2-methoxy-5 chlorobenzene and the diazoamino compound from diazotised 1-amino-2- methoxy-benzene-S-carboxylic. acid anilide with a secondary o-aminophenyl-carboxylic acid, generally with the aid of suitable assistants such as ethylene glycol, Monopol Brilliant Oil and sodium hydroxide solution, as well as of solubilisation promoting and stabilising aliphatic amines such as diethylamino-ethanol, and by padding it onto a fabric of cotton or regenerated cellulose on a foularding machine, drying and subsequently developing by a passage through acidic or neutral steam, organic acids such as formic acid or acetic acid or mixtures of organic acids being preferably employed for this purpose.

In order to prepare the discharge ground, the developed dyeing can now be overprinted with a white or colour discharge by the normal method. The usual washing operation follows the printing process. Brilliant white and coloured discharging effects are obtained on the red dyeing.

3,256,055 Patented June 14, 1966 "ice 5 or -5-sulphobenzene-Z-carboxylic acid, N-alkylor isobrilliant bluish-red discharge alkylaminobenzene-ocarboxylic acids such as l-carboxymethyl-aminobenZene-Z-carboxylic acid (phenylglycine-o-carboxylic acid), 3-chlorophenylglycine-o-carboxylic acid, 4-chlorophenylglycine-o-carboxylic acid, 5-chlorophenylglycine-o-carboxylic acid, 4,6-dichloro-, 3,4-dichloroor 3,6-dichloro-phenylglycine-o-carboxylic acid, 4-methoxy-phenylglycine-o-carboxylic acid, N-hydroxyethyl-anthranilic acid, N-methoxyethyl-anthranilic acid,

N-methyl-, ethylor butyl-anthranilic acid, N-phenylglycinelower alkyl ester-o-carboxylic acids, N-phenylglycine amide-o-carboxylic acid, 1-N-sulphomethyl-aminobenzene-Z-carboxylic acid,

and also the derivatives of the above mentioned products substituted by sulphonic acid amide, sulphone or cyano groups at the benzene nucleus.

The following example is given for the purpose of illustrating the invention, without, however, restricting it thereto.

Example A bleached and mercerised cotton fabric is padded on a 3-roll foularding machine with a liquor which contains, per litre in addition to Water:

60 g. of a mixture of approximately equimolar amounts of 1-(2,3'-hydroxynaphthoylamino)- -methoxy-5-chlorobenzene and the diazoamino compound from diazotised l-amino-Z-methoxy benzene 5 carboxylic acid anilide with 2-ethylamino-5-sulpho-benzoic acid,

50 g. of ethylene glycol,

30 g. of Monopole BrilliantOil (German Patent No.

40 g. of sodium hydroxide solution (38 B.), and

30 g. of diethylamino-ethanol. 1 The liquor is at a temperature of 30 C. The absorption of liquor by the fabric amounts to The fabric padded by this method is dried by a continuous process whereupon its colour turns to a goldenyellow shade. Thereafter, the fabric is steamed at 102 C. for 5 minutes in a steamer with continuous operation, into which a mixture of one part of formic acid and 4 parts of 50% acetic acid is introduced in the form of a line spray through an injector of acid-resistant material which is activated by steam. During this procedure, the dyestuff is developed and after the fabric leaves the steamer it exhibits a brilliant red shade.

The dyed fabric is then rinsed in water warmed to 20 C., soaped with boiling, then again rinsed first with water heated to 60 C. and thereafter with water at 10 C., and dried.

The dyeing obtained in accordance with the above directions is printed with a white discharge of the following composition on a Rouleaux printing machine immediately after it leaves the steamer.

White discharge:

400 g. of wheat starch-tragacanth thickener, 200 g. of sodium formaldehyde-sulphoxylate, 150 g. of water,

80 g. of potassium carbonate,

30 g. of a mixture of sodium naphthalene-sulphonate with sodium monobenzyl-sulphonate,

40 g. of 30% anthraquinone paste g. of 1:1 zinc oxide/water.

The resultant alkaline aqueous rinsed again and dried. is obtained.

The ground colour printed with the white discharge may also be printed with the following black printing paste immediately after the White discharge has been printed onto it:

120 g. of a mixture of 25 parts of carbon black and 13 parts of an emulsifying agent, 400 g. of a mixture of equal parts of (a) A copolymer from 70 parts of asymmetrical dichloroethene with 30 parts of butyl acrylate, and (b) A 10% solution of a basic polyurea compound prepared by condensing diethylenetramine, N,N- 'y,'y'-diaminopropyl-N-methyl-amine and 1,6-hexanediisocyanate (German Patent No. 851,550) in acetic acid, 50 g. of urea, 350 g. of a thickener,

50 g. of a 3% solution of methylcellulose, and 30 g. of a 30% solution of the condensation product of N,N,'y,'y' diaminopropyl N methylamine and epichlorhydrin in hydrochloric acid. 1000 g.

After printing, the fabric is dried as usual and steamed at 102 C. for 8 minutes in a steamer with continuous operation.

It is then introduced into a solution of 3 g. of sodium carbonate in water heated at 80 C. and treated in it for 2 minutes, thereafter rinsed in water heated at 60 C. and then at 20 C., soaped with boiling and again rinsed with warm water, first at 60 C. and then at 20 C. The fabric is then dried. The identical or similar results can be obtained by replacing the diazoamino compound specified in this example by the use of diazoamino compounds from diazotised l-amino-2-methoxy-benzene-S-carboxylic acid anilide and the other stabilising amines mentioned in the description. The assistants in the dyeing and printing mixtures may of course also be varied as required.

We claim:

1. Process for the production of a brilliant bluish red discharge ground resistant to chlorine on cellulose fabrics, which comprises dyeing cellulose fabrics with a mixture of substantially equimolar amount of 1-(2',3'-hydroxynaphthoylamino)-2-methoXy-5-chlorobenzene and the diazoamino compound from diazotised 1-amino-2-methoxybenzene-S-carboxylic acid anilide with a secondary o-aminophenyl-carboxylic acid, and then developing by the action of acidic or neutral steam.

2. Process according to claim 1, which comprises applying a diazoamino compound from diazotized 1- amino-Z-methoxy-benzene-S-carboxylic acid anilide and a stabilizing amine selected from the class consisting of l-methylan1ino-, l-ethylaminoand l-isopropylamino-4- and -5-sulphobenzene-2-carboxylic acid, l-carboxymethylamino-benzene-2-carboxylic acid, 3-chlorophenylglycine-o-carboxylic acid 4-chlorophenylglycine-o-carboxylic acid, 5-chlorophenylglycine-o-carboxylic acid; 4,6-dichloro-,

3,4-dichl-oroand 3,6-dichlorophenylglycine-o-carboxylic acid, 4-methoxy-phenylglycine-o-carboxylic acid, N-hydroxyethyl-anthanilic acid, N-methoxyethyl-anthranilic acid,

N-methyl-,

N-ethyland N-butyl-anthranilic acid,

N-phenylglycinclower alkyl ester-o-carboxylic acid, N-phenylglycine amide-o-carboxylic acid,

. l-N sulphomethylamino-benzene-Z-carboxylic acid.

3. Process according to claim 1, which comprises applying a diazoamino compound from diazotised l-amino- 2-methoxybenzene-S-carboxylic acid anilide with 2-ethylamino-S-sulphobenzoic acid.

4. Process for the production of dyeings on cellulose fabrics satisfactorily discharged to be, white or light colour, which comprises discharging the dyeing obtainable in accordance with claim 1 to a white or light colour.

5. Discharge ground on cellulose fabrics, obtained according to the process of claim 1.

No references cited.

NORMAN G. TORCHIN, Primary Examiner. J. HERBERT, Assistant Examiner. 

1. PROCESS FOR THE PRODUCTION OF A BRILLIANT BLUISH RED DISCHARGE GROUND RESISTANT TO CHLORINE ON CELLULOSE FABRICS, WHICH COMPRISES DYEING CELLULOSE FABRICS WITH A MIXTURE OF SUBSTANTIALLY EQUIMOLAR AMOUNT OF 1-(2''-3''-HYDROXYNAPHTHOYLAMINO)-2-METHOXY-5-CHLOROBENZENE AND THE DIAZOAMINO COMPOUND FROM DIAZOTISED 1-AMINO-2-METHOXYBENZENE-2-CARBOXYLIC ACID ANILIDE WITH A SECONDARY O-AMINOPHENYL-CARBOXYLIC ACID, AND THEN DEVELOPING BY THE ACTION OF ACIDIC OR NEUTRAL STEAM. 